Seasonal variations of PAHs content and distribution patterns in a mixed land use area: A case study in NE Italy with the transplanted lichen Pseudevernia furfuracea

The seasonal differences of the polycyclic aromatic hydrocarbons (PAHs) content in lichen transplants were investigated in an area of ca. 40 square kilometers in NE Italy characterized by different land use. Two sets of samples of the epiphytic lichen Pseudevernia furfuracea were collected in a pristine area of the Carnic Alps and transplanted to 40 exposure sites for a period of two months, respectively in late winter and in summer. Results revealed a pronounced difference between the two seasons in terms of PAH content and distribution patterns. After the summer exposure the PAH concentrations in the transplants were more than one order of magnitude lower than after the winter exposure (ranging from 48.22 to 272.73 ng g 121 dw and from 289.73 to 1575.85 ng g 121 dw in the summer and winter samples respectively). Also the main emission sources changed, mostly due to the drastic reduction in the emissions by wood burning for domestic heating and to the different meteorological conditions. In summer PAHs degradation was enhanced by intense UV radiation, high temperatures, and presence of ozone. The implications of these findings for the biomonitoring of PAHs pollution are addressed

Emissioni e assorbimento di composti organici in matrici ambientali

Questo studio si \ue8 focalizzato sulla valutazione delle emissioni di aerosol e composti organici volatili, sia antropogenici che biogenici, e delle dinamiche evolutive che determinano la composizione atmosferica di background in area giuliana. Sono state inoltre identificate le condizioni di campionamento e le matrici vegetali pi\uf9 idonee per il biomonitoraggio di microinquinanti. In primo luogo \ue8 stata svolta una caratterizzazione dell\u2019aerosol in un sito rurale del Carso triestino definendo le concentrazioni di macrocostituenti (ioni inorganici, carbonio organico ed elementare) e componenti minori, indici di combustione di biomasse (levoglucosano e Idrocarburi Policiclici Aromatici) o derivanti da fonti biogeniche (alcani dispari). \uc8 stata evidenziata una forte componente biogenica di particolato primario tipicamente legata al periodo vegetativo delle piante mentre la componente antropica \ue8 risultata limitata al periodo invernale. Uno studio di biomonitoraggio svolto con il gruppo di ricerca in lichenologia del Dipartimento di Scienze della Vita dell\u2019ateneo giuliano mediante trapianti di Pseudevernia furfuracea alle pendici delle pre-Alpi Carniche ha analogamente evidenziato concentrazioni di IPA significative solo nella stagione fredda e invece trascurabili nel periodo estivo sia per l\u2019assenza della sorgente riscaldamento, sia considerando la maggior degradazione associata a condizioni atmosferiche pi\uf9 ossidanti. In collaborazione con il Dipartimento di Agricoltura e Scienze Ambientali dell\u2019Universit\ue0 di Udine \ue8 inoltre stato verificato l\u2019accumulo invernale di IPA su piante per il verde pubblico (Elaeagnus x ebbingei, Ilex aquifolium, Laurus nobilis, Ligustrum japonicum, Photinia x fraserii e Viburnum lucidum) trapiantate in due siti della citt\ue0 di Udine. Si \ue8 potuto osservare in particolare un accumulo degli IPA pi\uf9 pesanti (pi\uf9 significativi dal punto di vista tossicologico) ed identificare Elaeagnus x ebbingei, Ligustrum japonicum e Laurus nobilis come specie pi\uf9 adatte all\u2019impiego in studi di bioaccumulo il quale risulta correlato alla densit\ue0 stomatica delle foglie. Essendo noto che le piante emettono in atmosfera considerevoli quantit\ue0 di sostanze organiche volatili (BVOC) che possono reagire in atmosfera dando origine a componenti biogeniche dell\u2019aerosol (BSOA) e non risultando disponibili in letteratura altri studi simili sull\u2019area carsica, sono stati approntati dei metodi analitici atti alla valutazione dei flussi emissivi di BVOC e metodi atti all\u2019individuazione di derivati ossidati degli stessi nel particolato atmosferico. Utilizzando la tecnica branch enclosure sono state studiate le emissioni stagionali e circadiane di specie vegetali autoctone (Cotinus coggygria, Quercus pubescens, Pinus nigra, Fraxinus ornus). Tra i composti identificati risulta rilevante l\u2019isoprene, emesso essenzialmente da Quercus pubescens nelle ore centrali della giornata. Tenuto conto di parametri specie-specifici, quali il Leaf Area Index e la copertura del territorio, sono stati stimati i flussi emissivi per l\u2019associazione Aristolochio luteae-Quercetum pubescentis, caratteristica del Carso costiero. I valori ottenuti per la scala locale sono stati confrontati con stime computazionali ottenute per aree di maggiori dimensioni implementando un modello specifico per le emissioni naturali. Fra le specie organiche secondarie riscontrate su campioni estivi del PM10 raccolto presso un sito rurale carsico si annoverano l\u2019acido ossalico derivante dall\u2019isoprene e l\u2019acido pinonico derivante dal pinene. In collaborazione con l\u2019Universit\ue0 di Aahrus sono anche stati analizzati composti secondari nitrossisolforati per i quali si \ue8 riscontrata una differenza significativa rispetto alle concentrazioni diurne e notturne indicando l\u2019importanza dei processi di ossidazione fotochimica che coinvolgono specie radicaliche azotate dovute all\u2019evoluzione long-range di emissioni antropiche quali NOx

Advances in TD/GC-MS untargeted compound analysis on particulate matter beyond PAHs routine monitoring

The monitoring of some micro-pollutants is routinary because of their potential toxic activity and of normative regulation, but focusing only on some targeted compounds can divert analysts and researchers from identifying pollution macro-events associated to untargeted compounds. Routine analysis of micro-pollutants, as PAHs, in fast scan GC-MS produces Single Ion Monitoring (SIM) chromatograms used for quantitative determination of target compounds but also a Total Ion Current (TIC) signal which can potentially contain interesting unrevealed information. This is specially true when thermal desorption from solid samples as air particulate matter filters is used as pretreatment method; TD/GC-MS transfers analytes to the separation column without discarding some/part of the compounds. The aim of this study is to report the setup of an experimental and data analysis procedure adequate for disclosing interesting data from raw GCMS data collections acquired during routine monitoring. In this communication we present a 3 month daily PAHs routine monitoring near an incinerator in a Friuli Venezia Giulia chair production district in which we collected 120 samples of PM10 by quartz filter sampling accordingly to EN12341. A series of raw data (retention time, peak area, peak height, peak width, MW, CAS number) were acquired directly from the data analysis software (meanwhile quantifying PAHs) using the \u201cautointegration\u201d and \u201cMS library search\u201d functions. These data were handled within R free statistical computing environment (http://cran.rproject. org), using a home-made script to filter and intercomparing chromatograms by peak properties. In this way we were able, starting from over 5000 peaks to discriminate, beyond PAHs, 21 relevant peaks present in a great number of samples. Using MS library search reports we were able to identify three molecules with high correspondence to the MS database, which can be related to activities in the sampling site: a plasticizer, a phtalate and an erbicide. These compounds were quantified using corresponding commercial standards

Derivatized volatile organic compound characterization of Friulano wine from Collio (Italy–Slovenia) by HS-SPME-GC-MS and discrimination from other varieties by chemometrics

Purpose Methods to assess the authenticity and traceability of wines have been extensively studied as enhancers of food quality, allowing producers to obtain market recognition and premium prices. Among analytical techniques, the volatilome profile attained by gas chromatography coupled with mass spectrometry is acquiring more and more attention by the scientific community, together with the use of chemometrics Design/methodology/approach The volatilome profile of three varieties of blanc wines from the Collio area (namely Ribolla Gialla, Malvasia and Friulano) between Italy and Slovenia, was determined by head space-solid phase micro extraction-gas chromatography-mass spectrometry, enhancing the carbonyl compounds identification with O-(2, 3, 4, 5, 6-pentafluorobenzyl)-hydroxylamine with the aim of identifying the autochthonous Friulano variety. Findings A two-step chemometric approach based on an unsupervised technique (PCA) followed by a supervised one (PLS-DA) allowed to identify possible markers for discriminating the Friulano Collio variety from the others, in particular two chemical classes were identified by PCA (ketones and long chain esters). PLS-DA showed 87% accuracy in classification. A correct classification (i.e. non-Friulano Collio) of a group of wines obtained from the same grape variety but produced in an extra-Collio area was obtained as well. The results confirmed the benefits of using a derivatization step prior to volatile organic compounds analysis. Research limitations/implications Among methods to assess the authenticity and traceability of wines, volatilome profile of wines determined by head space-solid phase micro extraction-gas chromatography-mass spectrometry, enhanced by the carbonyl compound identifications with O-(2, 3, 4, 5, 6-pentafluorobenzyl)-hydroxylamine, may have a key role in conjunction with chemometrics and, in particular with principal component analysis and partial least square discriminant analysis. Practical implications Among methods to assess the authenticity and traceability of Friulano wine, volatilome profile of wines determined by head space-solid phase micro extraction-gas chromatography-mass spectrometry, enhanced by the carbonyl compound identifications with O-(2, 3, 4, 5, 6-Pentafluorobenzyl)Hydroxylamine hydrochloride, may have a key role in conjunction with chemometrics. Originality/value Few works investigated both wine traceability with a volatilome enhancer and chemometrics of the Friulano wine variety obtaining such an improvement in this wine variety discrimination

Small scale spatial gradients of outdoor and indoor benzene in proximity of an integrated steel plant

Benzene is known as a human carcinogen, whose annual mean concentration exceeded the EU limit value (5 \u3bcg/m3) only in very few locations in Europe during 2012. Nevertheless 10% to 12% of the EU-28 urban population was still exposed to benzene concentrations above the WHO reference level of 1.7 \u3bcg/m3. WHO recommended a wise choice of monitoring stations positioning in proximity of \u201chot spots\u201d to define and assess the representativeness of each site paying attention to micro-scale conditions. In this context benzene and other VOCs of health concern (toluene, ethylbenzene, xylenes) concentrations have been investigated, with weekly passive sampling for one year, both in outdoor and indoor air in inhabited buildings in close proximity (180 m far up to 1100 m) of an integrated steel plant in NE of Italy. Even though the outdoor mean annual benzene concentration was below the EU limit in every site, in the site closest to the works the benzene concentration was above 5 \u3bcg/m3 in 14 weeks. These events were related to a benzene over toluene ratio above one, which is diagnostic for the presence of an industrial source, and to meteorological factors. These information pointed at the identification of the coke ovens of the plant as the dominant outdoor source of benzene. Benzene gradients with the increasing distance from coke ovens have been found for both outdoor and indoor air. Linear models linking outdoor to indoor benzene concentrations have been then identified, allowing to estimate indoor exposure from ambient air benzene data. In the considered period, a narrow area of about 250 m appeared impacted at a higher degree than the other sites both considering outdoor and indoor air. Passive BTEX sampling permits to collect information on both ambient air and daily life settings, allowing to assemble a valuable data support for further environmental cost-benefit analyses

Aerosol studies in the Karst of Trieste (Italy)

Regional air quality assessment and modeling of dynamics of gaseous and aerosol compounds can greatly benefit from experimental studies at sampling sites positioned in relative distance from intense sources of pollution; this is particularly valid in complex areas as the Karst, the limestone borderline plateau region extending in southwestern Slovenia and northeastern Italy, at some tens of kilometers from Trieste, a city of 210.000 inhabitants with an harbour, from the industrial town of Monfalcone with its 976 MW power plant and close to the Northern Adriatic Sea. A sampling site for aerosol and organic gases was established in Spring 2012 in close proximity to the entrance of the cave called Grotta Gigante, where also a meteorological station is working since 1967. The site lays in a submediterranean deciduous forest classified as Ostryo-Quercetum pubescentis. A day-night campaign was conducted in late June 2012 where ions, OC/EC and secundary organic compounds were measured, showing that the site is adequate to study BSOA formation from terpenes and isoprene precursors. Contrasts between summer and winter were studied with a series of four days samples, where ions, OC/EC, n-alkanes and PAHs were detected; markers from biomass burning as well as MSA, signing marine biogenic contribution, highlight the plurality of sources contributing at formation of aereosols. Recent XRF powder analysis contribute to mass closure, with information about inorganic composition. Experimental data are also compared with estimates from MEGAN model of emission of gas and aerosol from nature. Chemistry of wet and dry depositions has also started to be studied, aiming at characterizing inorganic inputs to soils